WO2017154851A1 - Composition d'électrolyte solide, feuille contenant un électrolyte solide, batterie rechargeable entièrement solide, procédé de production de composition d'électrolyte solide, procédé de production de feuille contenant un électrolyte solide, et procédé de fabrication de batterie rechargeable entièrement solide - Google Patents

Composition d'électrolyte solide, feuille contenant un électrolyte solide, batterie rechargeable entièrement solide, procédé de production de composition d'électrolyte solide, procédé de production de feuille contenant un électrolyte solide, et procédé de fabrication de batterie rechargeable entièrement solide Download PDF

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WO2017154851A1
WO2017154851A1 PCT/JP2017/008845 JP2017008845W WO2017154851A1 WO 2017154851 A1 WO2017154851 A1 WO 2017154851A1 JP 2017008845 W JP2017008845 W JP 2017008845W WO 2017154851 A1 WO2017154851 A1 WO 2017154851A1
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group
solid electrolyte
solid
secondary battery
active material
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PCT/JP2017/008845
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English (en)
Japanese (ja)
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雅臣 牧野
宏顕 望月
稔彦 八幡
智則 三村
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富士フイルム株式会社
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Priority to JP2018504482A priority Critical patent/JP6615313B2/ja
Priority to CN201780015831.8A priority patent/CN108780918B/zh
Publication of WO2017154851A1 publication Critical patent/WO2017154851A1/fr
Priority to US16/123,023 priority patent/US10833351B2/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a solid electrolyte composition, a solid electrolyte-containing sheet, and an all-solid secondary battery, and a solid electrolyte composition, a solid electrolyte-containing sheet, and an all-solid secondary battery manufacturing method.
  • a lithium ion secondary battery is a storage battery that has a negative electrode, a positive electrode, and an electrolyte sandwiched between the negative electrode and the positive electrode, and enables charging and discharging by reciprocating lithium ions between the two electrodes.
  • an organic electrolytic solution has been used as an electrolyte in a lithium ion secondary battery.
  • the organic electrolyte is liable to leak, and there is a possibility that a short circuit occurs inside the battery due to overcharge or overdischarge, resulting in ignition, and further improvements in reliability and safety are required. Under such circumstances, an all-solid secondary battery using an inorganic solid electrolyte instead of an organic electrolyte has been attracting attention.
  • All-solid-state secondary batteries are composed of a solid negative electrode, electrolyte, and positive electrode, which can greatly improve safety and reliability, which is a problem of batteries using organic electrolytes, and can also extend the life. It will be. Furthermore, the all-solid-state secondary battery can have a structure in which electrodes and an electrolyte are directly arranged in series. Therefore, it is possible to increase the energy density as compared with a secondary battery using an organic electrolyte, and application to an electric vehicle, a large storage battery, and the like is expected.
  • Non-patent Document 1 any one of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer is formed of an inorganic solid electrolyte and / or an active material and a binder particle such as a specific polymer compound. It has been proposed to form a material containing (binder).
  • a composition containing a sulfide solid electrolyte material, a monomer or oligomer having a double bond, and a binder composition having a radical polymerization initiator is applied, and radical polymerization is performed.
  • Patent Document 2 describes an all-solid secondary battery containing a solid electrolyte and a polymer containing polymer units having a nitrile group in a specific ratio in any layer.
  • An object of the present invention is to provide a solid electrolyte composition capable of improving the binding property between solid particles and improving cycle characteristics in an all-solid-state secondary battery. Moreover, this invention makes it a subject to provide the solid electrolyte containing sheet
  • a solid electrolyte composition containing an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table and a compound having an anionically polymerizable functional group containing an inorganic solid electrolyte having conductivity of metal ions belonging to Group 1 or Group 2 of the periodic table and a compound having an anionically polymerizable functional group.
  • R 1 ⁇ R 3 represents a monovalent electron-withdrawing group independently
  • R 4 is a bond site to the carbon atom to which R 3 and R 4 are attached is an electron-withdrawing
  • a divalent electron-withdrawing group is shown
  • Ra represents a hydrogen atom or an organic group.
  • X represents an m + n-valent linking group, m is an integer of 0 to 10, and n is an integer of 2 to 10.
  • R 1 and R 2 , R 3 and R 4 may be linked to each other to form a ring.
  • (11) A step of dispersing and solidifying the inorganic solid electrolyte in the presence of a dispersion medium; Adding the compound having an anion polymerizable functional group to the obtained slurry.
  • R 11A and R 12A each independently represent a monovalent electron withdrawing group
  • R 13B represents a monovalent electron withdrawing group or —R 14B — * 2
  • R 14B represents R A divalent electron withdrawing group in which the bonding site to the carbon atom to which 13B and R 14B are bonded is electron withdrawing. * 2 indicates a bond.
  • R 11A and R 12A , R 13B and R 14B may be linked to each other to form a ring.
  • An all-solid secondary battery comprising a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer in this order, An inorganic solid electrolyte in which at least one of the negative electrode active material layer, the solid electrolyte layer, and the positive electrode active material layer has conductivity of ions of metals belonging to Group 1 or Group 2 of the periodic table, and an inorganic solid electrolyte All-solid-state secondary battery containing the anion polymer which has a repeating unit represented by the following general formula (2A) or (2B) couple
  • R 11A and R 12A each independently represent a monovalent electron withdrawing group
  • R 13B represents a monovalent electron withdrawing group or —R 14B — * 2
  • R 14B represents R A divalent electron withdrawing group in which the bonding site to the carbon atom to which 13B and R 14B are bonded is electron withdrawing. * 2 indicates a bond.
  • R 11A and R 12A , R 13B and R 14B may be linked to each other to form a ring.
  • a method for producing an all-solid secondary battery wherein an all-solid secondary battery is produced via the method for producing a solid electrolyte-containing sheet according to (13) or (14).
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • acryl or “(meth) acryl” is simply described, it means methacryl and / or acryl.
  • the term “acryloyl” or “(meth) acryloyl” simply means methacryloyl and / or acryloyl.
  • substituents, etc. when there are a plurality of substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by specific symbols, or when a plurality of substituents etc. are specified simultaneously or alternatively, It means that a substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like.
  • the mass average molecular weight (Mw) can be measured as a molecular weight in terms of polystyrene by GPC.
  • GPC device HLC-8220 manufactured by Tosoh Corporation
  • G3000HXL + G2000HXL is used as the column
  • the flow rate is 1 mL / min at 23 ° C.
  • detection is performed by RI.
  • the eluent can be selected from THF (tetrahydrofuran), chloroform, NMP (N-methyl-2-pyrrolidone), m-cresol / chloroform (manufactured by Shonan Wako Pure Chemical Industries, Ltd.) and dissolves. If present, use THF.
  • the solid electrolyte composition of the present invention When used as a material for a solid electrolyte layer and / or an active material layer in an all-solid secondary battery, the solid electrolyte composition enhances the binding property between solid particles and is a solid resulting from repeated charge and discharge. It has an excellent effect of suppressing an increase in interfacial resistance between particles and improving cycle characteristics.
  • the solid electrolyte-containing sheet and the all-solid secondary battery of the present invention are excellent in binding properties and / or cycle characteristics.
  • seat, and an all-solid-state secondary battery can each be manufactured suitably.
  • the solid electrolyte composition of the present invention includes an inorganic solid electrolyte having conductivity of ions of metals belonging to Group 1 or Group 2 of the periodic table and a compound having an anion polymerizable functional group.
  • an inorganic solid electrolyte having conductivity of ions of metals belonging to Group 1 or Group 2 of the periodic table and a compound having an anion polymerizable functional group.
  • the solid electrolyte composition of the present invention contains an inorganic solid electrolyte.
  • the solid electrolyte of the inorganic solid electrolyte is a solid electrolyte that can move ions inside. Since it does not contain organic substances as the main ionic conductivity material, organic solid electrolytes (polymer electrolytes typified by polyethylene oxide (PEO), etc., and organics typified by lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), etc. It is clearly distinguished from the electrolyte salt). Further, since the inorganic solid electrolyte is solid in a steady state, it is not dissociated or released into cations and anions.
  • inorganic electrolyte salts LiPF 6 , LiBF 4 , lithium bis (fluorosulfonyl) imide (LiFSI), LiCl, etc.
  • LiPF 6 lithium bis (fluorosulfonyl) imide
  • LiFSI lithium bis (fluorosulfonyl) imide
  • LiCl LiCl
  • the inorganic solid electrolyte is not particularly limited as long as it has conductivity of ions of metal elements belonging to Group 1 or Group 2 of the periodic table, and generally does not have electron conductivity.
  • the inorganic solid electrolyte preferably has an ionic conductivity of lithium ions.
  • inorganic solid electrolyte a solid electrolyte material usually used for an all-solid secondary battery can be appropriately selected and used.
  • Typical examples of inorganic solid electrolytes include (i) sulfide-based inorganic solid electrolytes and (ii) oxide-based inorganic solid electrolytes.
  • a sulfide-based inorganic solid An electrolyte is preferably used.
  • the sulfide-based inorganic solid electrolyte contains a sulfur atom (S) and has ionic conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table, And what has electronic insulation is preferable.
  • the sulfide-based inorganic solid electrolyte preferably contains at least Li, S, and P as elements and has lithium ion conductivity. However, depending on the purpose or the case, other than Li, S, and P may be used. An element may be included.
  • a lithium ion conductive inorganic solid electrolyte satisfying the composition represented by the following formula (1) can be mentioned and is preferable.
  • L represents an element selected from Li, Na and K, and Li is preferred.
  • M represents an element selected from B, Zn, Sn, Si, Cu, Ga, Sb, Al, and Ge. Among these, B, Sn, Si, Al, or Ge is preferable, and Sn, Al, or Ge is more preferable.
  • A represents I, Br, Cl or F, preferably I or Br, and particularly preferably I.
  • L, M, and A can each be one or more of the above elements.
  • a1 to e1 indicate the composition ratio of each element, and a1: b1: c1: d1: e1 satisfies 1 to 12: 0 to 1: 1: 2 to 12: 0 to 5.
  • a1 is further preferably 1 to 9, and more preferably 1.5 to 4.
  • b1 is preferably 0 to 0.5.
  • d1 is preferably 3 to 7, and more preferably 3.25 to 4.5.
  • e1 is preferably 0 to 3, more preferably 0 to 1.
  • the composition ratio of each element can be controlled by adjusting the blending amount of the raw material compound when producing the sulfide-based inorganic solid electrolyte.
  • the sulfide-based inorganic solid electrolyte may be amorphous (glass) or crystallized (glass ceramic), or only a part may be crystallized.
  • glass glass
  • glass ceramic glass ceramic
  • Li—PS system glass containing Li, P, and S or Li—PS system glass ceramics containing Li, P, and S can be used.
  • the sulfide-based inorganic solid electrolyte includes [1] lithium sulfide (Li 2 S) and phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), [2] lithium sulfide and at least one of simple phosphorus and simple sulfur, Or [3] It can be produced by the reaction of lithium sulfide, phosphorus sulfide (for example, diphosphorus pentasulfide (P 2 S 5 )), at least one of elemental phosphorus and elemental sulfur.
  • the ratio of Li 2 S to P 2 S 5 in the Li—PS system glass and Li—PS system glass ceramic is a molar ratio of Li 2 S: P 2 S 5 , preferably 65:35 to 85:15, more preferably 68:32 to 77:23.
  • the lithium ion conductivity can be further increased.
  • the lithium ion conductivity can be preferably 1 ⁇ 10 ⁇ 4 S / cm or more, more preferably 1 ⁇ 10 ⁇ 3 S / cm or more. Although there is no particular upper limit, it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • the sulfide-based inorganic solid electrolyte include, for example, those using a raw material composition containing Li 2 S and a sulfide of an element belonging to Group 13 to Group 15. it can. More specifically, Li 2 S—P 2 S 5 , Li 2 S—LiI—P 2 S 5 , Li 2 S—LiI—Li 2 O—P 2 S 5 , Li 2 S—LiBr—P 2 S 5 , Li 2 S—Li 2 O—P 2 S 5 , Li 2 S—Li 3 PO 4 —P 2 S 5 , Li 2 S—P 2 S 5 —P 2 O 5 , Li 2 S—P 2 S 5- SiS 2 , Li 2 S—P 2 S 5 —SnS, Li 2 S—P 2 S 5 —Al 2 S 3 , Li 2 S—GeS 2 , Li 2 S—GeS 2 —ZnS, Li 2 S— Ga 2 S 3 , Li 2 S—GeS 2 —G
  • Examples of a method for synthesizing a sulfide-based inorganic solid electrolyte material using such a raw material composition include an amorphization method.
  • Examples of the amorphization method include a mechanical milling method and a melt quenching method, and among them, the mechanical milling method is preferable. This is because processing at room temperature is possible, and the manufacturing process can be simplified. Among these, Li 2 S—P 2 S 5 , LGPS (Li 10 GeP 2 S 12 ), Li 2 S—P 2 S 5 —SiS 2 and the like are preferable.
  • the oxide-based inorganic solid electrolyte contains an oxygen atom (O) and has ionic conductivity of a metal element belonging to Group 1 or Group 2 of the periodic table, And what has electronic insulation is preferable.
  • the oxide-based inorganic solid electrolyte preferably has an ionic conductivity of 1 ⁇ 10 ⁇ 6 S / cm or more, more preferably 5 ⁇ 10 ⁇ 6 S / cm or more, and 1 ⁇ 10 ⁇ 5 S. / Cm or more is particularly preferable.
  • the upper limit is not particularly limited, but it is practical that it is 1 ⁇ 10 ⁇ 1 S / cm or less.
  • Li xa La ya TiO 3 [xa satisfies 0.3 ⁇ xa ⁇ 0.7, and ya satisfies 0.3 ⁇ ya ⁇ 0.7.
  • LLT Li xb La yb Zr zb M bb mb Onb
  • M bb is one or more elements selected from Al, Mg, Ca, Sr, V, Nb, Ta, Ti, Ge, In and Sn
  • Xb satisfies 5 ⁇ xb ⁇ 10
  • yb satisfies 1 ⁇ yb ⁇ 4
  • zb satisfies 1 ⁇ zb ⁇ 4
  • mb satisfies 0 ⁇ mb ⁇ 2
  • nb satisfies 5 ⁇ nb ⁇ 20.
  • Li xc B yc M cc zc Onc (M cc is one or more elements selected from C, S, Al, Si, Ga, Ge, In and Sn.
  • Xc is 0 ⁇ xc ⁇ 5
  • Yc satisfies 0 ⁇ yc ⁇ 1,
  • zc satisfies 0 ⁇ zc ⁇ 1,
  • nc satisfies 0 ⁇ nc ⁇ 6
  • Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P md Ond (xd satisfies 1 ⁇ xd ⁇ 3, yd Satisfies 0 ⁇ yd ⁇ 1, zd satisfies 0 ⁇ zd ⁇ 2, ad satisfies 0 ⁇ ad ⁇ 1, md satisfies 1 ⁇ md ⁇ 7, and nd satisfies 3 ⁇
  • Li, P and O Phosphorus compounds containing Li, P and O are also desirable.
  • lithium phosphate Li 3 PO 4
  • LiPON obtained by substituting a part of oxygen of lithium phosphate with nitrogen
  • LiPOD 1 (D 1 is preferably Ti, V, Cr, Mn, Fe, Co, Ni, And at least one element selected from Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and Au.
  • LiA 1 ON (A 1 is one or more elements selected from Si, B, Ge, Al, C, and Ga) can be preferably used.
  • LLT Li xb La yb Zr zb M bb mb O nb
  • LLZ Li 3 BO 3, Li 3 BO 3 -Li 2 SO 4 and Li xd (Al, Ga) yd (Ti, Ge) zd Si ad P md O nd (xd, yd, zd, ad, md and nd are as defined above.)
  • LLZ, LLT LAGP Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3
  • LATP [Li 1.4 Ti 2 Si 0.4 P 2.6 O 12 ] —AlPO 4 ) are more preferable.
  • the inorganic solid electrolyte is preferably a particle.
  • the volume average particle diameter of the particulate inorganic solid electrolyte is not particularly limited, but is preferably 0.01 ⁇ m or more, and more preferably 0.1 ⁇ m or more. As an upper limit, it is preferable that it is 100 micrometers or less, and it is more preferable that it is 50 micrometers or less.
  • the measurement of the volume average particle diameter of an inorganic solid electrolyte is performed in the following procedures.
  • the inorganic solid electrolyte particles are prepared by diluting a 1 mass% dispersion in a 20 mL sample bottle using water (heptane in the case of a substance unstable to water).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that.
  • a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA)
  • data was acquired 50 times using a quartz cell for measurement at a temperature of 25 ° C., Obtain the volume average particle size.
  • JISZ8828 2013 “Particle Size Analysis—Dynamic Light Scattering Method” is referred to as necessary. Five samples are prepared for each level, and the average value is adopted.
  • the content of the inorganic solid electrolyte in the solid electrolyte composition should be 5% by mass or more at a solid content of 100% by mass considering the reduction of interface resistance and the effect of maintaining battery characteristics (improvement of cycle characteristics). Is more preferable, 70% by mass or more is more preferable, and 90% by mass or more is particularly preferable. As an upper limit, it is preferable that it is 99.9 mass% or less from the same viewpoint, It is more preferable that it is 99.5 mass% or less, It is especially preferable that it is 99 mass% or less.
  • the content of the inorganic solid electrolyte in the solid electrolyte composition is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more.
  • the content of the inorganic solid electrolyte in the solid electrolyte composition is such that the total content of the positive electrode active material or the negative electrode active material and the inorganic solid electrolyte is within the above range. Is preferred.
  • solid content refers to a component that does not volatilize or evaporate when subjected to a drying treatment at 170 ° C. for 6 hours in a nitrogen atmosphere. Typically, it refers to components other than the dispersion medium described below.
  • An inorganic solid electrolyte may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the solid electrolyte composition of the present invention contains a compound having an anion polymerizable functional group.
  • Anionic polymerizability refers to the property that monomer units form bonds continuously through an anion addition reaction using an anion as a polymerization initiation species.
  • the radical polymerizable property, anionic polymerizable property, and cationic polymerizable property of a vinyl monomer are determined by the resonance stabilization of the substituent bonded to the vinyl group and the effect of polarity.
  • the Qe scheme quantifies this as an empirical parameter.
  • Q represents the conjugation effect of the monomer (degree of resonance stabilization), and e represents the polar effect of the monomer.
  • a monomer having a Q value of 2.0 or more and an e value of 0.8 or more tends to exhibit anionic polymerizability.
  • monomers having a Q value of 4.0 or more and an e value of 0.9 or more are more likely to exhibit anionic polymerizability.
  • the practical upper limit value is a Q value of 15 or less and an e value of 4.0 or less.
  • the compound having an anion polymerizable functional group used in the present invention is preferably a vinyl monomer having the above preferable Q value and e value, and a compound having the vinyl monomer having the above preferable Q value and e value as a substituent.
  • the compound having an anion polymerizable functional group used in the present invention more preferably satisfies the following condition 1 or 2, and is further represented by the following general formula (1a) or (1b). preferable.
  • the anionic polymerizable functional group used in the present invention forms a direct covalent bond with the inorganic solid electrolyte
  • the all-solid secondary battery produced using the solid electrolyte composition of the present invention is excellent. Show binding properties and cycle characteristics.
  • R 1A and R 2A each independently represent a monovalent electron withdrawing group
  • R 3B represents a monovalent electron withdrawing group or —R 4B — * 1
  • R 4B represents R A divalent electron withdrawing group in which the bonding site to the carbon atom to which 3B and R 4B are bonded is electron withdrawing is shown.
  • * 1 represents a bond as an anion polymerizable functional group.
  • R 1A and R 2A , R 3B and R 4B may be linked to each other to form a ring.
  • the compound having an anion polymerizable functional group that satisfies the above condition 2 may have a group represented by the general formula (1B) in any of the compounds.
  • Examples of the mode include a monofunctional compound having one or more groups represented by the above general formula (1B) and a polyfunctional compound having two or more groups in the compound.
  • the polymer which has group represented by the said General formula (1B) in a polymer principal chain and / or a side chain is mentioned. From the viewpoint of synthesis, a polymer having a group represented by the general formula (1B) in the polymer side chain is preferably exemplified.
  • the polymer may have any structure as long as the effect of the present invention is exhibited, and may be any copolymer of random, alternating, block and graft, for example.
  • the polymer chain is not limited to a carbon-carbon bond, and may have an amide bond, an ester bond, a urethane bond, a urea bond, or the like.
  • the monovalent electron withdrawing groups in R 1A , R 2A and R 3B are stable when handling the solid electrolyte composition, and when the solid electrolyte composition is applied. From the viewpoint of compatibility with curability, each independently, a nitro group, a cyano group, —C ( ⁇ O) OR 5 , —C ( ⁇ O) R 6 , an alkyl group substituted with a fluoro group, and a nitro group , A cyano group, —C ( ⁇ O) OR 5 , —C ( ⁇ O) R 6 and an aryl group substituted with at least one of a fluoro group are preferable.
  • R 5 and R 6 each independently represent a hydrogen atom, an alkyl group or an aryl group.
  • the description of the substituent P described later can be preferably applied.
  • the more preferable number of carbon atoms of the monovalent electron-withdrawing group and the substituents in R 5 and R 6 are shown below.
  • the number of substituents is not particularly limited, and is preferably 1 or more, and is preferably equal to or less than the number of hydrogen atoms of the alkyl group before being substituted. ⁇ 5 are more preferred, and 1 to 3 are more preferred.
  • the number of carbon atoms constituting the alkyl group is preferably 1 to 16, more preferably 1 to 12, still more preferably 1 to 8, particularly preferably 1 to 6, and most preferably 1 to 3.
  • the alkyl group substituted with a fluoro group in R 1 to R 3 is preferably a perfluoroalkyl group.
  • the number of substituents is not particularly limited, and 1 It is preferably at least one and not more than the number of hydrogen atoms of the aryl group before substitution, more preferably 1 to 5.
  • the number of carbon atoms constituting the aryl group is preferably 6 to 18, more preferably 6 to 14, and particularly preferably 6 to 12.
  • Substituent position numbers are preferably 2-position, 4-position and / or 6-position in the phenyl group, and more preferably 4-position.
  • an aryl group substituted with at least one of a nitro group, a cyano group and a fluoro group is preferred, and a phenyl group substituted with at least one of a nitro group, a cyano group and a fluoro group is preferred.
  • the alkyl group in R 5 and R 6 is an alkyl group (the number of carbon atoms is preferably 1-20, more preferably 1-16, still more preferably 1-8, particularly preferably 1-6, and most preferably 1-3). ), A cycloalkyl group (preferably having 3 to 20 carbon atoms) and an aralkyl group (preferably having 7 to 23 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-octyl, dodecyl, heptadecyl, cyclohexyl, isobornyl and benzyl.
  • the alkyl group may be either an unsubstituted alkyl group or a substituted alkyl group.
  • the aryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples include phenyl, tolyl and naphthyl.
  • the aryl group may be either an unsubstituted aryl group or a substituted aryl group.
  • Preferred examples of the substituted aryl group include aryl groups substituted with the above-described fluoro group.
  • R 5 and R 6 are each independently a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom or an alkyl group.
  • R 5 and R 6 are more preferably an alkyl group, and particularly preferably an alkyl group substituted with at least one functional group selected from the following functional group group I.
  • the functional group means both a functional group such as a hydroxy group and a bond such as an amide bond.
  • the acid anhydride group means a group obtained from an acid anhydride of a dicarboxylic acid (a group in which at least one hydrogen atom is replaced with a bond “—”).
  • the amino group preferably has 0 to 12 carbon atoms, more preferably 0 to 6 carbon atoms, and particularly preferably 0 to 2 carbon atoms.
  • the sulfonic acid group may be its ester or salt. In the case of an ester, the number of carbon atoms is preferably 1-24, more preferably 1-12, and particularly preferably 1-6.
  • the phosphate group may be its ester or salt. In the case of an ester, the number of carbon atoms is preferably 1-24, more preferably 1-12, and particularly preferably 1-6.
  • the preferable description of the substituent P mentioned later can be applied.
  • the said functional group may exist as a substituent or may exist as a coupling group.
  • the amino group may exist as a divalent imino group or a trivalent nitrogen atom.
  • the group having three or more ring structures is preferably a group having a cholesterol ring structure or a group having a structure in which three or more aromatic groups are condensed, and more preferably a cholesterol residue or a pyrenyl group.
  • the functional group selected from the functional group group is preferably any one of a hydroxy group, a carboxy group, a sulfonic acid group, a phosphoric acid group, a cyano group, an alkoxy group, and a group having a ring structure of three or more rings.
  • a carboxy group, a sulfonic acid group, a phosphoric acid group, and a group having three or more ring structures are more preferable.
  • Divalent electron withdrawing group The divalent electron withdrawing group in R 4B is substituted with * —C ( ⁇ O) OR 7 —, * —C ( ⁇ O) R 8 —, a fluoro group. And an arylene group substituted with at least one of a nitro group, a cyano group, —C ( ⁇ O) OR 5 , —C ( ⁇ O) R 6 and a fluoro group.
  • R 5 and R 6 has the same meaning as R 5 and R 6 in a monovalent electron-withdrawing group described above
  • R 7 and R 8 represents a single bond each independently, an alkylene group or an arylene group Show.
  • the divalent electron-withdrawing group in R 4B includes an electron bonded site with a carbon atom to which R 3B and R 4B are bonded, in which one hydrogen atom in the substituent P described later is replaced with a bond “-”.
  • the description of a divalent group that is attractive can be preferably applied.
  • the more preferable carbon number etc. of the bivalent electron withdrawing group in R 4B are shown below.
  • the number of substituents is not particularly limited, and it is preferably 1 or more and less than or equal to the number of hydrogen atoms of the alkylene group before substitution. ⁇ 4 are more preferred, and 1-2 are even more preferred.
  • the number of carbon atoms constituting the alkylene group is preferably 1 to 16, more preferably 1 to 12, still more preferably 1 to 8, particularly preferably 1 to 6, and most preferably 1 to 3.
  • the alkylene group substituted with the fluoro group in R 4B is preferably a perfluoroalkylene group.
  • the number of substituents is not particularly limited.
  • the number of hydrogen atoms is preferably not more than the number of hydrogen atoms of the arylene group before substitution, and more preferably 1 to 4.
  • the number of carbon atoms constituting the arylene group is preferably 6 to 18, more preferably 6 to 14, and particularly preferably 6 to 12.
  • the substituent position number in the phenylene group, when the number of the free valence carbon bonded to the carbon atom to which R 3B and R 4B are bonded is 1, it is substituted at the 2-position, 4-position or 6-position. It preferably has a group, and more preferably has a substituent in at least one of the 2-position and 4-position. Of these, an arylene group substituted with at least one of a nitro group, a cyano group and a fluoro group is preferable, and a phenylene group substituted with at least one of a nitro group, a cyano group and a fluoro group is preferable.
  • the alkylene group for R 7 and R 8 preferably has 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. Most preferred. Specific examples include methylene, ethylene, n-propylene, isopropylene, n-butylene, t-butylene and n-octylene.
  • the alkylene group may be either an unsubstituted alkylene group or a substituted alkylene group. Preferred examples of the substituted alkylene group include an alkylene group substituted with the above-described fluoro group.
  • the arylene group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples include phenylene, tolylene, and naphthalenediyl.
  • the arylene group may be either an unsubstituted arylene group or a substituted arylene group. Preferred examples of the substituted arylene group include an arylene group substituted with the above-described fluoro group.
  • R 7 is a single bond, an alkylene group or an arylene group, and preferably a single bond or an alkylene group.
  • R 8 is preferably a single bond or an alkylene group.
  • R 1A is any one of a cyano group, a trifluoromethyl group, and —C ( ⁇ O) OR 5
  • R 2A is —C ( ⁇ O) OR 5
  • R 3B is preferably a monovalent electron-withdrawing group
  • particularly preferred combinations of R 3B and R 4B are those in which R 3B is a cyano group, a trifluoromethyl group, and —C ( ⁇ O) OR 5 .
  • R 4B is * —C ( ⁇ O) OR 7 —.
  • a compound having an anion polymerizable functional group having such a combination of substituents can achieve both stability when handling the solid electrolyte composition and curability when applying the solid electrolyte composition.
  • R 1 ⁇ R 3 represents a monovalent electron-withdrawing group independently
  • R 4 is a bond site to the carbon atom to which R 3 and R 4 are attached is an electron-withdrawing
  • a divalent electron-withdrawing group is shown
  • Ra represents a hydrogen atom or an organic group.
  • X represents an m + n-valent linking group, m is an integer of 0 to 10, and n is an integer of 2 to 10.
  • R 1 and R 2 , R 3 and R 4 may be linked to each other to form a ring.
  • the monovalent electron-withdrawing group in R 1 to R 3 and the divalent electron-withdrawing group in R 4 are the monovalent electron-withdrawing group and divalent groups in the general formulas (1A) and (1B). It is synonymous with the electron withdrawing group.
  • R a examples include an alkyl group, an aryl group, —C ( ⁇ O) OR b, and —C ( ⁇ O) R c .
  • R a is preferably a hydrogen atom, an alkyl group or —C ( ⁇ O) R c, more preferably an alkyl group or —C ( ⁇ O) R c .
  • R b and R c are preferably an alkyl group substituted with at least one functional group selected from the following functional group II.
  • the description in the functional group I can be preferably applied.
  • n is preferably an integer of 2 to 60, and more preferably an integer of 2 to 10.
  • m is preferably an integer of 0 to 10, more preferably an integer of 0 to 4.
  • X is preferably a 2 to 60 valent organic group, more preferably a 3 to 12 valent organic group.
  • n + m-valent linking group in X examples include polycyclic organic groups represented by the following general formulas (Q-1) to (Q-19), and the following general formulas (Q-20) to (Q-38).
  • Cyclic siloxane residues represented by the following general formulas (H-1) to (H-3) such as pentaerythritol residues, dipentaerythritol residues, diaminoalkylene residues and trimethylolalkane residues represented by Preferred examples include silsesquioxane residues represented by general formulas (P-1) to (P-8).
  • Y in the following general formulas (Q-1) to (Q-38) and R in the following general formulas (H-1) to (H-3) and (P-1) to (P-8) are arbitrary. And represents a binding site with R 4 or R a .
  • the arbitrary linking group is, for example, a single bond, an alkylene group (the number of carbon atoms is preferably 1-18, more preferably 1-10), —O—, —C ( ⁇ O) —, —C ( ⁇ O ) O— and —S—, and a single bond, an alkylene group or —O— is preferable.
  • a to f represent the number of repetitions, each independently preferably 2 to 20, more preferably 3 to 10.
  • the compound having an anion polymerizable functional group satisfying the above condition 1 include, for example, 2-methylenemalononitrile, H 2 C ⁇ C (COOR 5 ) 2 (2-methylenemalonic acid, dimethyl 2-methylenemalonate Diethyl 2-methylenemalonate, diisopropyl 2-methylenemalonate, butyl 2-methylenemalonate, t-butyl 2-methylenemalonate and cyclohexyl 2-methylenemalonate), H 2 C ⁇ C (CN) (COOR 5 ) (2-cyanoacrylic acid, methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, propyl 2-cyanoacrylate, isopropyl 2-cyanoacrylate, butyl 2-cyanoacrylate, benzyl 2-cyanoacrylate Methoxyethyl 2-cyanoacrylate, t-butyl 2-cyanoacrylate, 2 Isobornyl cyanoacrylate, cyclohexyl 2-cyanoacrylate, dode
  • the compound having an anion polymerizable functional group that satisfies the above condition 2 include the following compounds, but the present invention is not construed as being limited thereto.
  • the numerical value next to the parenthesis represents the mass ratio.
  • a substituent that does not specify substitution or non-substitution means that the group may have an appropriate substituent. This is also synonymous for compounds that do not specify substituted or unsubstituted.
  • Preferable substituents include the following substituent P. Examples of the substituent P include the following.
  • alkyl group preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.
  • alkenyl A group preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like
  • a cycloalkyl group preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc., but in this specification,
  • an aryloyl group (preferably an aryloyl group having 7 to 23 carbon atoms, such as benzoyl, etc., but an acyl group in this specification usually means an aryloyl group).
  • An acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy), an aryloyloxy group (preferably an aryloyloxy group having 7 to 23 carbon atoms, such as benzoyloxy, etc., provided that In this specification, an acyloxy group usually means an aryloyloxy group), a carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.
  • An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.), an alkylsulfanyl group (preferably an alkylsulfanyl group having 1 to 20 carbon atoms, such as methylsulfanyl, ethyl Sulfanyl, isopropyl Sulfanyl, benzylsulfanyl, etc.), arylsulfanyl groups (preferably arylsulfanyl groups having 6 to 26 carbon atoms, such as phenylsulfanyl, 1-naphthylsulfanyl, 3-methylphenylsulfanyl, 4-methoxyphenylsulfanyl, etc.), alkylsulfonyl A group (preferably an alkylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl or ethyls
  • a silyl group (preferably an alkylsilyl group having 1 to 20 carbon atoms, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc.), an arylsilyl group (preferably 6 to 4 carbon atoms)
  • Arylsilyl groups such as triphenylsilyl
  • alkoxysilyl groups preferably alkoxysilyl groups having 1 to 20 carbon atoms such as monomethoxysilyl, dimethoxysilyl, trimethoxysilyl, triethoxysilyl, etc.
  • aryl An oxysilyl group (preferably an aryloxysilyl group having 6 to 42 carbon atoms, such as triphenyloxysilyl), a phosphoryl group (preferably a phosphoryl group having 0 to 20 carbon atoms, such as —OP ( ⁇ O) (R P ) 2 ), a phosphonyl group (preferably a phosphonyl
  • Groups such as -P (R P ) 2 ), (meth) acryloyl groups, (meth) acryloyloxy groups, ( (Meth) acryloylumimino group ((meth) acrylamide group), hydroxy group, sulfanyl group, carboxy group, phosphoric acid group, phosphonic acid group, sulfonic acid group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, Iodine atom).
  • each of the groups listed as the substituent P may be further substituted with the substituent P described above.
  • substituent, linking group and the like include an alkyl group, an alkylene group, an alkenyl group, an alkenylene group, an alkynyl group and / or an alkynylene group, these may be cyclic or linear, and may be linear or branched. It may be substituted as described above or unsubstituted.
  • the compound having an anion polymerizable functional group used in the present invention is preferably a compound having two or more anion polymerizable functional groups represented by the general formula (1B), and is represented by the general formula (1b). Is more preferable. Since these compounds having an anion polymerizable functional group have two or more anion polymerizable functional groups in one molecule, a strong cross-linked product by anionic polymerization, that is, a hard cured film is formed. It is preferable from the viewpoint that the life can be improved.
  • the compound having an anion polymerizable functional group represented by the general formula (1A) or (1a) is, for example, purified by distillation after acid-chlorinating the corresponding anion polymerizable carboxylic acid in the presence of thionyl chloride or phthalic acid dichloride. It can be obtained by esterification by treating with 2,6-lutidine and alcohols.
  • the compound having an anion polymerizable functional group represented by the general formula (1b) can be synthesized, for example, by the following method. That is, a compound in which the terminal portion in X which is a mother nucleus of a multi-branched skeleton (star type, hyperbranch type and dendrimer type) is a nucleophilic functional group such as hydroxy group, carboxy group, amino group and mercapto group, Alternatively, for a compound having a leaving group such as a halogen atom (Cl, Br, I), —OTs, and —OMs, a reactive functional group (hydroxyl group) between the anion polymerizable functional group and the terminal portion of X of the compound.
  • a compound having a leaving group such as a halogen atom (Cl, Br, I), —OTs, and —OMs
  • Ts represents a tosyl group and Ms represents a mesyl group.
  • an anion represented by the general formula (1b) is formed by forming an ester bond from a reaction of a hydroxy group and a carboxy group, an amide bond from a reaction of an amino group and a carboxy group, and a thioester bond from a reaction of a mercapto group and a carboxy group. A compound having a polymerizable functional group is obtained.
  • a compound having an anion polymerizable functional group represented by the general formula (1b) is formed.
  • a compound having an anion polymerizable functional group represented by the above general formula (1B) is also processed in the same manner as the compound having an anion polymerizable functional group represented by the above general formula (1b). Can be synthesized.
  • the molecular weight of the compound having an anion polymerizable functional group used in the present invention is preferably from 100 to 200,000, more preferably from 100 to 5,000, from the viewpoint of anionic polymerization rate and / or crosslinking rate and non-volatility. Preferably, 100 to 1,000 is more preferable.
  • the molecular weight means a mass average molecular weight. The mass average molecular weight can be measured using, for example, GPC.
  • the content of the compound having an anion-polymerizable functional group used in the present invention in the solid electrolyte composition is 5 at a solid content of 100% by mass from the viewpoint of hardly inhibiting ionic conductivity while giving sufficient binding properties. Less than 3% by mass is preferable, less than 3% by mass is more preferable, and less than 2% by mass is particularly preferable. Although there is no restriction
  • the compounds having an anion polymerizable functional group used in the present invention may be used singly or in combination of two or more.
  • a combination of the above H 2 C ⁇ C (CN) (COOR 5 ) and the above H 2 C ⁇ C (CF 3 ) (COOR 5 ) is preferable, and cyanoacrylate and trifluoromethyl acrylate A combination is most preferred.
  • the content of the anionic polymerizable functional group having a cyano group in all anionic polymerizable functional groups is preferably 0 to 2% by mass or more than 30% by mass and 100% by mass or less, and more than 30% by mass. More preferably, it is 100 mass% or less.
  • the solid electrolyte composition of the present invention may contain other functional additives described later.
  • the all-solid-state secondary battery formed using the solid electrolyte composition containing the compound having an anion polymerizable functional group used in the present invention exhibits high binding properties and excellent cycle characteristics as described above.
  • the solid electrolyte composition of the present invention preferably contains a particle dispersant.
  • the particle dispersant is a positive active material or a negative active material, and an organic compound that is unevenly distributed on the surface by chemical bonding or physical adsorption, and preferably has a reactive unsaturated bond.
  • the compound having an anion polymerizable functional group used in the present invention in combination with a particle dispersant having a reactive unsaturated bond capable of anion addition, and the binding property between the inorganic solid electrolyte and the active material. Can be further increased, which is preferable. This is because the reactive unsaturated bond capable of anion addition in the particle dispersing agent is added to the growth terminal of the compound having an anion polymerizable functional group to form a covalent bond, so that there is a gap between the inorganic solid electrolyte and the active material. This is considered to be due to covalent linkage through an anionic polymer.
  • the particle dispersant is composed of a low molecular weight or oligomer having a molecular weight of 70 or more and less than 3000, and preferably contains at least one functional group represented by the following functional group group (A). It is more preferable that it comprises an oligomer and contains at least one functional group represented by the following functional group group (A) and the above-mentioned reactive unsaturated bond capable of anion addition in the same molecule.
  • acidic group for example, carboxy group, sulfonic acid group, phosphoric acid group
  • group having basic nitrogen atom for example, alkoxysilyl group, epoxy group, oxetanyl group, isocyanate group, cyano group, sulfanyl group , A hydroxy group and a condensed hydrocarbon group having three or more rings (for example, a pyrenyl group)
  • the molecular weight of the particle dispersant is preferably 70 or more and less than 3000, more preferably 100 or more and less than 2000, and still more preferably 500 or more and less than 1000. If the molecular weight is too large, particles are likely to aggregate and the output of the all-solid-state secondary battery may be reduced. On the other hand, if the molecular weight is too small, it tends to volatilize when the solid electrolyte composition is applied and dried. In the case of an oligomer, the molecular weight means a mass average molecular weight. The mass average molecular weight can be measured using, for example, GPC.
  • an acidic group a group having a basic nitrogen atom, a cyano group, and a condensed hydrocarbon group having three or more rings are preferable, and an acidic group, a group having a basic nitrogen atom, and a cyano group are preferable. More preferred is an acidic group. Of the acidic groups, a carboxy group is most preferred.
  • Examples of the group having an unsaturated bond capable of anion addition of the particle dispersant include (meth) acryloyl group, (meth) acrylamide group, vinyl group and styryl group, which are preferable.
  • Specific examples of the particle dispersant include (meth) acrylic acid, (meth) acrylic acid (2-pyrenyl) methyl, erythritol tetraacrylate partially modified carboxylic acid (acrylate 3-substituted, carboxylic acid 1-substituted) and dipenta Preferred examples include carboxylic acid partially modified erythritol hexamethacrylate (methacrylate 4-substituted, carboxylic acid 2-substituted).
  • grain dispersing agent may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the content in the solid electrolyte composition is preferably 0.1% by mass or more, and 0.5% by mass or more at a solid content of 100% by mass. It is more preferable that the content is 1% by mass or more.
  • the upper limit of the content is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less. preferable.
  • the solid electrolyte composition of the present invention preferably contains a binder.
  • the binder used in the present invention is not particularly limited as long as it is an organic polymer.
  • the binder that can be used in the present invention is preferably a binder that is usually used as a binder for a positive electrode or a negative electrode of a battery material, and is not particularly limited.
  • a binder made of a resin described below is preferable.
  • fluorine-containing resin examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP), and the like.
  • thermoplastic resin examples include polyethylene, polypropylene, styrene butadiene rubber (SBR), hydrogenated styrene butadiene rubber (HSBR), butylene rubber, acrylonitrile butadiene rubber (also referred to as butadiene-acrylonitrile copolymer), polybutadiene, polyisoprene, and the like. Is mentioned.
  • acrylic resin examples include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate isopropyl, poly (meth) acrylate isobutyl, poly (meth) butyl acrylate, poly (meth) ) Hexyl acrylate, poly (meth) acrylate octyl, poly (meth) acrylate dodecyl, poly (meth) acrylate stearyl, poly (meth) acrylate 2-hydroxyethyl, poly (meth) acrylic acid, poly (meth) ) Benzyl acrylate, poly (meth) acrylate glycidyl, poly (meth) acrylate dimethylaminopropyl, and copolymers of monomers constituting these resins.
  • copolymers with other vinyl monomers are also preferably used.
  • examples thereof include (meth) methyl acrylate-styrene copolymer, (meth) methyl acrylate-acrylonitrile copolymer, (meth) butyl acrylate-acrylonitrile-styrene copolymer, and the like.
  • a polycondensation polymer can also be used.
  • the polycondensation polymer for example, urethane resin, urea resin, amide resin, imide resin, polyester resin, and the like can be suitably used.
  • the polycondensation polymer preferably has a hard segment part and a soft segment part.
  • the hard segment site indicates a site capable of forming an intermolecular hydrogen bond
  • the soft segment site generally indicates a flexible site having a glass transition temperature (Tg) of room temperature (25 ⁇ 5 ° C.) or lower and a molecular weight of 400 or higher. These may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the upper limit of the glass transition temperature of the binder is preferably 50 ° C. or lower, more preferably 0 ° C. or lower, and most preferably ⁇ 20 ° C. or lower.
  • the lower limit is preferably ⁇ 100 ° C. or higher, more preferably ⁇ 70 ° C. or higher, and particularly preferably ⁇ 50 ° C. or higher.
  • the glass transition temperature (Tg) is measured under the following conditions using a dry sample and a differential scanning calorimeter “X-DSC7000” (trade name, manufactured by SII Nanotechnology Co., Ltd.). The measurement is performed twice on the same sample, and the second measurement result is adopted.
  • Measurement chamber atmosphere Nitrogen (50 mL / min) Temperature increase rate: 5 ° C / min Measurement start temperature: -100 ° C Measurement end temperature: 200 ° C
  • Sample pan Aluminum pan Mass of measurement sample: 5 mg Calculation of Tg: Tg is calculated by rounding off the decimal point of the intermediate temperature between the lowering start point and the lowering end point of the DSC chart.
  • the water concentration of the polymer constituting the binder is preferably 100 ppm (mass basis) or less, and Tg is preferably 100 ° C. or less.
  • the solvent used for the polymerization reaction of the polymer is not particularly limited. It is desirable to use a solvent that does not react with the inorganic solid electrolyte and the active material and that does not decompose them.
  • a solvent that does not react with the inorganic solid electrolyte and the active material and that does not decompose them.
  • hydrocarbon solvents toluene, heptane, xylene
  • ester solvents ethyl acetate, propylene glycol monomethyl ether acetate
  • ether solvents tetrahydrofuran, dioxane, 1,2-diethoxyethane
  • ketone solvents acetone
  • Methyl ethyl ketone Methyl ethyl ketone, cyclohexanone
  • nitrile solvents acetonitrile, propionitrile, butyronitrile, isobutyronitrile
  • halogen solvents dichloromethane
  • the polymer constituting the binder preferably has a mass average molecular weight of 10,000 or more, more preferably 20,000 or more, and further preferably 50,000 or more. As an upper limit, 1,000,000 or less is preferable, 200,000 or less is more preferable, and 100,000 or less is more preferable. In the present invention, the molecular weight of the polymer means a mass average molecular weight unless otherwise specified.
  • the content of the binder in the solid electrolyte composition is 0.01% by mass with respect to 100% by mass of the solid component, considering good reduction in interface resistance and its maintainability when used in an all-solid secondary battery.
  • the above is preferable, 0.1% by mass or more is more preferable, and 1% by mass or more is more preferable.
  • the mass ratio [(mass of inorganic solid electrolyte + mass of electrode active material) / mass of binder] of the total mass (total amount) of the inorganic solid electrolyte and the electrode active material to be included if necessary with respect to the mass of the binder is: A range of 1,000 to 1 is preferred. This ratio is more preferably 500 to 2, and further preferably 100 to 10.
  • the binder is a polymer particle that maintains the particle shape.
  • poly (meth) methyl acrylate (PMMA), methyl methacrylate-methacrylic acid copolymer (PMMA-PMA) or methyl methacrylate-ethyl methacrylate phosphate copolymer (PMMA-PHM) is preferably used. It is done.
  • the “polymer particles” refer to particles that do not completely dissolve even when added to the dispersion medium described later, and are dispersed in the dispersion medium in the form of particles and exhibit an average particle diameter of more than 0.01 ⁇ m.
  • the shape of the polymer particles is not limited as long as they are solid.
  • the polymer particles may be monodispersed or polydispersed.
  • the polymer particles may be spherical or flat and may be amorphous.
  • the surface of the polymer particles may be smooth or may have an uneven shape.
  • the polymer particles may have a core-shell structure, and the core (inner core) and the shell (outer shell) may be made of the same material or different materials. Moreover, it may be hollow and the hollow ratio is not limited.
  • the polymer particles can be synthesized by a method of polymerizing in the presence of a surfactant, an emulsifier or a dispersant, or a method of depositing in a crystalline form with an increase in molecular weight. Moreover, you may use the method of crushing the existing polymer mechanically, or the method of making a polymer liquid fine particle by reprecipitation.
  • the average particle diameter of the polymer particles is preferably 0.01 ⁇ m to 100 ⁇ m, more preferably 0.05 ⁇ m to 50 ⁇ m, further preferably 0.1 ⁇ m to 20 ⁇ m, and particularly preferably 0.2 ⁇ m to 10 ⁇ m.
  • the average particle diameter of the polymer particles used in the present invention is based on the measurement conditions and definitions described below.
  • the polymer particles are diluted and prepared in a 20 ml sample bottle using an arbitrary solvent (dispersion medium used for preparing the solid electrolyte composition, for example, heptane).
  • the diluted dispersion sample is irradiated with 1 kHz ultrasonic waves for 10 minutes and used immediately after that.
  • a laser diffraction / scattering particle size distribution measuring device LA-920 (trade name, manufactured by HORIBA)
  • data was acquired 50 times using a quartz cell for measurement at a temperature of 25 ° C., Let the obtained volume average particle diameter be an average particle diameter.
  • JISZ8828 2013 “Particle Size Analysis—Dynamic Light Scattering Method” is referred to as necessary. Five samples are prepared for each level and measured, and the average value is adopted. In addition, the measurement from the produced all-solid-state secondary battery is performed, for example, after disassembling the battery and peeling off the electrode, then measuring the electrode material according to the method for measuring the average particle diameter of the polymer particles, This can be done by eliminating the measured value of the average particle diameter of the particles other than the polymer particles that have been measured.
  • a commercial item can be used for the binder used for this invention. Moreover, it can also prepare by a conventional method.
  • the solid electrolyte composition of the present invention preferably contains a dispersion medium.
  • the dispersion medium should just be what disperse
  • Examples of the alcohol compound solvent include methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, Examples include 2-methyl-2,4-pentanediol, 1,3-butanediol, and 1,4-butanediol.
  • ether compound solvents examples include alkylene glycol alkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene.
  • alkylene glycol alkyl ethers ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene.
  • Glycol monomethyl ether tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.
  • dialkyl ethers dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, etc.
  • cyclic ethers tetrahydrofuran, geo Sun (1,2, including 1,3- and 1,4-isomers of), etc.
  • Examples of the amide compound solvent include N, N-dimethylformamide, N-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
  • Examples of the amino compound solvent include triethylamine, diisopropylethylamine, tributylamine and the like.
  • Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • Examples of the aromatic compound solvent include benzene, toluene, xylene, mesitylene and the like.
  • Examples of the aliphatic compound solvent include hexane, heptane, octane, decane, and the like.
  • Examples of the nitrile compound solvent include acetonitrile, propyronitrile, isobutyronitrile, and the like.
  • ester compound solvent examples include ethyl acetate, butyl acetate, propyl acetate, butyl butyrate, and butyl pentanoate.
  • non-aqueous dispersion medium examples include the above aromatic compound solvents and aliphatic compound solvents.
  • amino compound solvents, ether compound solvents, ketone compound solvents, aromatic compound solvents, and aliphatic compound solvents are preferable, and ether compound solvents, aromatic compound solvents, and aliphatic compound solvents are more preferable.
  • the dispersion medium preferably has a boiling point of 50 ° C. or higher, more preferably 70 ° C. or higher, at normal pressure (1 atm).
  • the upper limit is preferably 250 ° C. or lower, and more preferably 220 ° C. or lower.
  • the said dispersion medium may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the content of the dispersion medium in the solid electrolyte composition can be appropriately set in consideration of the balance between the viscosity of the solid electrolyte composition and the drying load. Generally, it is preferably 20 to 99% by mass, more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass in the solid electrolyte composition.
  • the solid electrolyte composition of the present invention may contain an active material capable of inserting and releasing ions of metal elements belonging to Group 1 or Group 2 of the periodic table.
  • the active material includes a positive electrode active material and a negative electrode active material, and a transition metal oxide that is a positive electrode active material or a metal oxide that is a negative electrode active material is preferable.
  • a solid electrolyte composition containing an active material positive electrode active material, negative electrode active material
  • an electrode layer composition positive electrode layer composition, negative electrode layer composition.
  • the positive electrode active material that may be contained in the solid electrolyte composition of the present invention is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and may be a transition metal oxide or an element that can be complexed with Li such as sulfur.
  • the positive electrode active material it is preferable to use a transition metal oxide, and a transition metal oxide having a transition metal element M a (one or more elements selected from Co, Ni, Fe, Mn, Cu and V). More preferred.
  • this transition metal oxide includes an element M b (an element of the first (Ia) group of the metal periodic table other than lithium, an element of the second (IIa) group, Al, Ga, In, Ge, Sn, Pb, Elements such as Sb, Bi, Si, P or B) may be mixed.
  • the mixing amount is preferably 0 ⁇ 30 mol% relative to the amount of the transition metal element M a (100mol%). Those synthesized by mixing so that the molar ratio of Li / Ma is 0.3 to 2.2 are more preferable.
  • transition metal oxide examples include (MA) a transition metal oxide having a layered rock salt structure, (MB) a transition metal oxide having a spinel structure, (MC) a lithium-containing transition metal phosphate compound, (MD And lithium-containing transition metal halide phosphate compounds and (ME) lithium-containing transition metal silicate compounds.
  • transition metal oxide having a layered rock salt structure LiCoO 2 (lithium cobaltate [LCO]), LiNi 2 O 2 (lithium nickelate) LiNi 0.85 Co 0.10 Al 0.05 O 2 (lithium nickel cobalt aluminate [NCA]), LiNi 1/3 Co 1/3 Mn 1/3 O 2 (nickel manganese lithium cobaltate [NMC]) and LiNi 0.5 Mn 0.5 O 2 (manganese) Lithium nickelate).
  • transition metal oxides having (MB) spinel structure include LiCoMnO 4, Li 2 FeMn 3 O 8 , Li 2 CuMn 3 O 8 , Li 2 CrMn 3 O 8 and Li 2 NiMn 3 O 8. .
  • Examples of (MC) lithium-containing transition metal phosphate compounds include olivine-type phosphate iron salts such as LiFePO 4 and Li 3 Fe 2 (PO 4 ) 3 , iron pyrophosphates such as LiFeP 2 O 7 , LiCoPO 4, and the like. And monoclinic Nasicon type vanadium phosphate salts such as Li 3 V 2 (PO 4 ) 3 (vanadium lithium phosphate).
  • (MD) as the lithium-containing transition metal halogenated phosphate compound for example, Li 2 FePO 4 F such fluorinated phosphorus iron salt, Li 2 MnPO 4 hexafluorophosphate manganese salts such as F and Li 2 CoPO 4 F Cobalt fluorophosphates such as
  • Examples of the (ME) lithium-containing transition metal silicate compound include Li 2 FeSiO 4 , Li 2 MnSiO 4, and Li 2 CoSiO 4 .
  • a transition metal oxide having a (MA) layered rock salt structure is preferable, and LCO, NMC or NMC is more preferable.
  • the shape of the positive electrode active material is not particularly limited, but is preferably particulate.
  • the volume average particle diameter (sphere conversion average particle diameter) of the positive electrode active material is not particularly limited.
  • the thickness can be 0.1 to 50 ⁇ m.
  • an ordinary pulverizer or classifier may be used.
  • the positive electrode active material obtained by the firing method may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.
  • the volume average particle diameter (sphere-converted average particle diameter) of the positive electrode active material particles can be measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (trade name, manufactured by HORIBA).
  • the positive electrode active materials may be used alone or in combination of two or more.
  • the mass (mg) (weight per unit area) of the positive electrode active material per unit area (cm 2 ) of the positive electrode active material layer is not particularly limited. It can be determined appropriately according to the designed battery capacity.
  • the content of the positive electrode active material in the solid electrolyte composition is not particularly limited, and is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, and even more preferably 50 to 85% by mass at 100% by mass. Preferably, it is 55 to 80% by mass.
  • the negative electrode active material that may be contained in the solid electrolyte composition of the present invention is preferably one that can reversibly insert and release lithium ions.
  • the material is not particularly limited as long as it has the above characteristics, and is a carbonaceous material, a metal oxide such as tin oxide, a silicon oxide, a metal composite oxide, a lithium simple substance and a lithium alloy such as a lithium aluminum alloy, and , Metals such as Sn, Si, and In that can form an alloy with lithium.
  • a carbonaceous material or a lithium composite oxide is preferably used from the viewpoint of reliability.
  • the metal composite oxide is preferably capable of inserting and extracting lithium.
  • the material is not particularly limited, but preferably contains titanium and / or lithium as a constituent component from the viewpoint of high current density charge / discharge characteristics.
  • the carbonaceous material used as the negative electrode active material is a material substantially made of carbon.
  • various synthetics such as petroleum pitch, carbon black such as acetylene black (AB), graphite (natural graphite, artificial graphite such as vapor-grown graphite), PAN (polyacrylonitrile) -based resin, furfuryl alcohol resin, etc.
  • the carbonaceous material which baked resin can be mentioned.
  • various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA (polyvinyl alcohol) -based carbon fiber, lignin carbon fiber, glassy carbon fiber, and activated carbon fiber. Examples thereof include mesophase microspheres, graphite whiskers, and flat graphite.
  • an amorphous oxide is particularly preferable, and chalcogenite, which is a reaction product of a metal element and an element of Group 16 of the periodic table, is also preferably used. It is done.
  • amorphous as used herein means an X-ray diffraction method using CuK ⁇ rays, which has a broad scattering band having a peak in the region of 20 ° to 40 ° in terms of 2 ⁇ , and is a crystalline diffraction line. You may have.
  • the strongest intensity of crystalline diffraction lines seen from 2 ° to 40 ° to 70 ° is 100 times the diffraction line intensity at the peak of the broad scattering band seen from 2 ° to 20 °. It is preferable that it is 5 times or less, and it is particularly preferable not to have a crystalline diffraction line.
  • an amorphous oxide of a metalloid element and a chalcogenide are more preferable.
  • Ga, Si, Sn, Ge, Pb, Sb and Bi are used alone or in combination of two or more thereof, and chalcogenides are particularly preferable.
  • preferable amorphous oxides and chalcogenides include, for example, Ga 2 O 3 , SiO, GeO, SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 2 O 4 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 8 Bi 2 O 3 , Sb 2 O 8 Si 2 O 3 , Bi 2 O 4 , SnSiO 3 , GeS, SnS, SnS 2 , PbS, PbS 2 , Sb 2 S 3 , Sb 2 S 5 and SnSiS 3 are preferred. Moreover, these may be a complex oxide with lithium oxide, for example, Li 2 SnO 2 .
  • the negative electrode active material contains a titanium atom. More specifically, Li 4 Ti 5 O 12 (lithium titanate [LTO]) is excellent in rapid charge / discharge characteristics due to small volume fluctuations during the insertion and release of lithium ions, and the deterioration of the electrodes is suppressed, and the lithium ion secondary This is preferable in that the battery life can be improved.
  • Li 4 Ti 5 O 12 lithium titanate [LTO]
  • hard carbon or graphite is preferably used, and graphite is more preferably used.
  • the said carbonaceous material may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the shape of the negative electrode active material is not particularly limited, but is preferably particulate.
  • the average particle size of the negative electrode active material is preferably 0.1 to 60 ⁇ m.
  • a normal pulverizer or classifier is used.
  • a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling air flow type jet mill, and a sieve are preferably used.
  • pulverizing wet pulverization in the presence of water or an organic solvent such as methanol can be performed as necessary.
  • classification is preferably performed.
  • the classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be used both dry and wet.
  • the average particle diameter of the negative electrode active material particles can be measured by the same method as the above-described method for measuring the volume average particle diameter of the positive electrode active material.
  • the chemical formula of the compound obtained by the above firing method can be calculated from an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measurement method, and from a mass difference between powders before and after firing as a simple method.
  • ICP inductively coupled plasma
  • Examples of the negative electrode active material that can be used in combination with the amorphous oxide negative electrode active material centered on Sn, Si, and Ge include carbon materials that can occlude and release lithium ions or lithium metal, lithium, lithium alloys, and lithium. An alloyable metal is preferable.
  • a Si-based negative electrode it is preferable to apply a Si-based negative electrode.
  • a Si negative electrode can occlude more Li ions than a carbon negative electrode (such as graphite and acetylene black). That is, the amount of Li ion occlusion per unit weight increases. Therefore, the battery capacity can be increased. As a result, there is an advantage that the battery driving time can be extended.
  • the said negative electrode active material may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the mass (mg) (weight per unit area) of the negative electrode active material per unit area (cm 2 ) of the negative electrode active material layer is not particularly limited. It can be determined appropriately according to the designed battery capacity.
  • the content of the negative electrode active material in the solid electrolyte composition is not particularly limited, and is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, and more preferably 30 to 80% at a solid content of 100% by mass. More preferably, it is 40% by weight, and still more preferably 40-75% by weight.
  • the surface of the positive electrode active material and / or the negative electrode active material may be surface-coated with a surface coating agent.
  • the surface coating agent include metal oxides containing Ti, Nb, Ta, W, Zr, Si, or Li, and specifically include titanate spinel, tantalum oxide, niobium oxide, and the like. Examples thereof include lithium niobate compounds. More specifically, Li 4 Ti 5 O 12 , LiTaO 3 , LiNbO 3 , LiAlO 2 , Li 2 ZrO 3 , Li 2 WO 4 , Li 2 TiO 3 , Li 2 B 4 O 7 , Li 3 PO 4 , Li 2 MoO 4 and LiBO 2 and the like.
  • the electrode surface containing a positive electrode active material and / or a negative electrode active material may be surface-treated with sulfur, phosphorus, or the like.
  • the solid electrolyte composition of the present invention may appropriately contain a conductive aid used for improving the electronic conductivity of the active material, as necessary.
  • a conductive aid used for improving the electronic conductivity of the active material
  • a general conductive auxiliary agent can be used.
  • electronic conductive materials such as graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black and furnace black, amorphous carbon such as needle coke, vapor grown carbon fiber and carbon nanotube Carbon fibers such as graphene and carbonaceous materials such as graphene and fullerene, metal powders such as copper and nickel, or metal fibers may be used, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene and polyphenylene derivatives May be used. Moreover, 1 type of these may be used and 2 or more types may be used.
  • the solid electrolyte composition of the present invention contains a conductive aid, the content of the conductive aid
  • the solid electrolyte composition of the present invention preferably contains a lithium salt (supporting electrolyte).
  • a lithium salt usually used in this type of product is preferably used without particular limitation, and examples thereof include the lithium salt described in the binder particles.
  • This lithium salt is not included in the binder particles (the polymer forming the binder particles) (for example, it is present alone in the solid electrolyte layer composition), and the lithium salt is included in the binder particles. Is different.
  • the content of the lithium salt is preferably 0 part by mass or more and more preferably 5 parts by mass or more with respect to 100 parts by mass of the solid electrolyte. As an upper limit, 50 mass parts or less are preferable, and 20 mass parts or less are more preferable.
  • the method for producing a solid electrolyte composition of the present invention includes a step (a1) of dispersing an inorganic solid electrolyte in the presence of a dispersion medium to form a slurry, and adding a compound having an anion polymerizable functional group to the obtained slurry.
  • Step (b1) Slurry in the step (a1) can be performed by mixing the inorganic solid electrolyte and the dispersion medium using various mixers.
  • the mixing apparatus is not particularly limited, and examples thereof include a ball mill, a bead mill, a planetary mixer, a blade mixer, a roll mill, a kneader, and a disk mill.
  • the mixing conditions are not particularly limited. For example, when a ball mill is used, the mixing is preferably performed at 150 to 700 rpm (rotation per minute) for 1 to 24 hours.
  • step (b1) it is preferable to mix a compound having an anion polymerizable functional group into the slurry, and the above mixing apparatus can be used.
  • the mixing conditions are not particularly limited as long as the compound having an anion polymerizable functional group is not cured by the progress of anion polymerization. For example, when a ball mill is used, mixing is performed at 50 to 200 rpm (rotation per minute) for 1 to 30 minutes. It is preferable to do.
  • a solid electrolyte composition containing other components such as a particle dispersant, it is preferable to add and mix it with the inorganic solid electrolyte and the dispersion medium before step (b1). It is more preferable to disperse together with the inorganic solid electrolyte.
  • a solid electrolyte composition containing an active material When preparing a solid electrolyte composition containing an active material, it is preferably added and mixed to the resulting slurry after step (a1), together with a compound having an anionically polymerizable functional group in step (b1). It is more preferable to mix.
  • Storage of the prepared solid electrolyte composition is not particularly limited as long as curing due to the progress of anionic polymerization does not occur, but 35 ° C. or less (more preferably 25 ° C. or less, more preferably less than 5 ° C.) after preparation. It is preferable to store in Moreover, it is preferable to use it for preparation of a solid electrolyte containing sheet and / or preparation of an all-solid secondary battery within one month (5 ° C. storage) after preparation.
  • the compound having an anion-polymerizable functional group used in the present invention is advancing anion polymerization using an anionic functional group present on the surface of the inorganic solid electrolyte and / or active material (preferably the surface of the solid particle) as an anionic polymerization initiating species.
  • an anionic polymer hereinafter also referred to as an anionic polymer.
  • PS 4 3- in Li 3 PS 4 and P 3 S 11 7- in Li 7 P 3 S 11 may become an anionic polymerization initiation species, and oxidation if -based, for example, Li 7 La 3 Zr 2 O 12 in (LLT) (La 3 Zr 2 O 12) 7- , but also, Li 5 La 3 Ta 2 O 12 in (LLZ) (La 3 Ta 2 O 12 ) 5- can be an anionic polymerization initiating species.
  • an anionic polymerization initiation step a covalent bond is formed between the inorganic solid electrolyte and the anionic polymer, and a stronger binding property is expressed.
  • an inorganic solid electrolyte and a polymer having a high molecular weight are added, a bond is not formed between the inorganic solid electrolyte and the polymer, and thus high binding properties cannot be exhibited.
  • the solid electrolyte composition of the present invention can also contain an anionic polymerization initiator for the purpose of promoting anionic polymerization.
  • the anionic polymerization initiator is not particularly limited as long as it can generate anions.
  • strong anionic polymerization initiators include potassium, alkyl (aryl) potassium, sodium, alkyl (aryl) sodium, lithium, alkyl (aryl) lithium, Grignard reagent, dialkyl (aryl) magnesium, trialkyl (aryl) aluminum, Examples include dialkyl zinc, alkoxy (aryloxy) potassium, alkoxy (aryloxy) sodium, alkoxy (aryloxy) lithium, alkylthio (arylthio) potassium, alkylthio (arylthio) sodium and alkylthio (arylthio) lithium.
  • weak anionic polymerization initiators include pyridines, amines, carboxylic acids, carboxylic acid metal salts, thiocarboxylic acid metal salts, alkylthiols, and water.
  • the addition amount is preferably from 0.1 mol% to 10 mol%, more preferably from 1 mol% to 3 mol%, based on the compound having an anion polymerizable functional group.
  • a polymer is formed.
  • An anionic polymer has a chemical bond between solid particle surfaces, such as an inorganic solid electrolyte.
  • R 11A and R 12A each independently represent a monovalent electron withdrawing group
  • R 13B represents a monovalent electron withdrawing group or —R 14B — * 2
  • R 14B represents R A divalent electron withdrawing group in which the bonding site to the carbon atom to which 13B and R 14B are bonded is electron withdrawing. * 2 indicates a bond.
  • R 11A and R 12A , R 13B and R 14B may be linked to each other to form a ring.
  • R 11A , R 12A , R 13B and R 14B in the general formulas (2A) and (2B) have the same meaning as R 1A , R 2A , R 3B and R 4B in the general formulas (1A) and (1B). is there. Note that * 2 in the above general formula (2B) is a bond corresponding to * 1 in the above general formula (1B).
  • anionic polymerization of the compound having an anion polymerizable functional group represented by the above general formula (1a) or (1b) proceeds, whereby the repeating unit represented by the following general formula (2a) or (2b) An anionic polymer having is formed.
  • An anionic polymer has a chemical bond between solid particle surfaces, such as an inorganic solid electrolyte.
  • R 11 and R 12 are each independently substituted with a nitro group, a cyano group, —C ( ⁇ O) OR 15 , —C ( ⁇ O) R 16 , an alkyl group substituted with a fluoro group, or a fluoro group.
  • R 15 and R 16 each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group or an acyl group.
  • R 11 and R 12 may be linked to form a ring.
  • Z represents a group represented by the following general formula (2b-z).
  • R a1 represents a hydrogen atom or an organic group
  • X 1 is shows the m 1 + n 1 valent linking group
  • m 1 is an integer of 0 ⁇ 10
  • n 1 is an integer of 2-10.
  • R 13 has the same meaning as R 11 .
  • R 14 represents * —C ( ⁇ O) OR 17 —, * —C ( ⁇ O) R 18 —, an alkylene group substituted with a fluoro group or an arylene group substituted with a fluoro group, and R 17 and R 18 Each independently represents a single bond, an alkylene group or an arylene group.
  • * Indicates a bonding site to the carbon atom to which R 13 and R 14 are bonded.
  • R 13 and R 14 may be linked to form a ring. ** indicates the binding site on the X 1.
  • R 11 to R 18 and each substituent in R a1 are R 1 to R 8 in the above general formulas (1a) and (1b). And the description of each substituent in R a can be preferably applied. Further, n 1 , m 1 and X 1 in the general formula (2b) have the same meanings as n, m and X in the general formula (1b).
  • Anionic polymerization may be started in any step of a grinding step using a ball mill for preparing the composition, a heating step different from the composition preparation, and a step of heating the coating film of the composition. It is preferable that the reaction is completed (cured) in the state of the solid electrolyte-containing sheet.
  • the conditions commonly used in anionic polymerization can be used as the polymerization conditions for the compound having an anion polymerizable functional group.
  • the reaction temperature is preferably 50 ° C. to 180 ° C., more preferably 80 ° C. to 150 ° C.
  • the reaction time is preferably 5 minutes to 3 hours, more preferably 10 minutes to 1 hour. .
  • anionic polymer used in the present invention are preferably anionic polymers having the following structural units, but the present invention is not limited thereto.
  • the numerical value next to the parenthesis represents the mass ratio.
  • Solid electrolyte-containing sheet has an inorganic solid electrolyte having conductivity of ions of metals belonging to Group 1 or Group 2 of the periodic table, and a specific repeating unit that binds to the inorganic solid electrolyte described above.
  • Anionic polymer Anionic polymer.
  • the anionic polymer is preferably an anionic polymer having a repeating unit represented by the above general formula (2A) or (2B), and an anionic polymer having a repeating unit represented by the above general formula (2a) or (2b). Coalescence is more preferred.
  • the content of the repeating unit containing a cyano group is preferably 0 to less than 2% by mass or more than 30% by mass and 100% by mass or less, and more than 30% by mass and 100% by mass or less. More preferred.
  • the repeating unit containing a cyano group is a repeating unit in which R 11A and / or R 12A in the general formula (2A) has a cyano group, and a cyano group in R 13B and / or R 14B in the general formula (2B).
  • the solid electrolyte-containing sheet of the present invention may contain the other functional additives described above.
  • the content of the anionic polymer in the solid electrolyte-containing sheet is preferably less than 5% by mass at a solid content of 100% by mass, considering the reduction in interfacial resistance and the effect of maintaining battery characteristics (improving cycle characteristics). It is more preferably less than 3% by mass, further preferably less than 2% by mass, particularly preferably less than 1.5% by mass, and most preferably less than 1.2% by mass. Although there is no restriction
  • the solid electrolyte-containing sheet of the present invention can be suitably used for an all-solid-state secondary battery, and includes various modes depending on the application.
  • a sheet preferably used for a solid electrolyte layer also referred to as a solid electrolyte sheet for an all-solid secondary battery
  • a sheet preferably used for an electrode or a laminate of an electrode and a solid electrolyte layer an electrode sheet for an all-solid secondary battery Etc.
  • these various sheets may be collectively referred to as an all-solid secondary battery sheet.
  • the all-solid-state secondary battery sheet is a sheet having a solid electrolyte layer or an active material layer (electrode layer) on a base material.
  • the all-solid-state secondary battery sheet may have other layers as long as it has a substrate and a solid electrolyte layer or an active material layer. It classifies into a secondary battery electrode sheet. Examples of other layers include a protective layer, a current collector, and a coat layer (current collector, solid electrolyte layer, active material layer) and the like.
  • Examples of the solid electrolyte sheet for an all-solid secondary battery include a sheet having a solid electrolyte layer and a protective layer in this order on a base material.
  • the substrate is not particularly limited as long as it can support the solid electrolyte layer, and examples thereof include the materials described in the above current collector, sheet bodies (plate-like bodies) such as organic materials and inorganic materials, and the like.
  • the organic material include various polymers, and specific examples include polyethylene terephthalate, polypropylene, polyethylene, and cellulose.
  • the inorganic material include glass and ceramic.
  • the configuration and layer thickness of the solid electrolyte layer of the all-solid-state secondary battery sheet are the same as the configuration and layer thickness of the solid electrolyte layer described later in the all-solid-state secondary battery of the present invention.
  • This sheet is obtained by forming (coating and drying) the solid electrolyte composition of the present invention on a base material (which may be via another layer) to form a solid electrolyte layer on the base material. It is done.
  • the solid electrolyte composition of the present invention can be prepared by the above-described method.
  • the electrode sheet for an all-solid secondary battery of the present invention is a metal as a current collector for forming the active material layer of the all-solid-state secondary battery of the present invention.
  • This electrode sheet is usually a sheet having a current collector and an active material layer, but an embodiment having a current collector, an active material layer, and a solid electrolyte layer in this order, and a current collector, an active material layer, and a solid electrolyte The aspect which has a layer and an active material layer in this order is also included.
  • the configuration and the layer thickness of each layer constituting the electrode sheet are the same as the configuration and the layer thickness of each layer described later in the all solid state secondary battery of the present invention.
  • the electrode sheet is obtained by forming (coating and drying) the solid electrolyte composition containing the active material of the present invention on a metal foil to form an active material layer on the metal foil.
  • the method for preparing the solid electrolyte composition containing the active material is the same as the method for preparing the solid electrolyte composition except that the active material is used.
  • the compound having an anion polymerizable functional group is preferably read as an anionic polymer with respect to the component species to be contained and the content ratio thereof. Otherwise, it is the same as that in the solid content of the solid electrolyte composition.
  • the all solid state secondary battery of the present invention has a positive electrode, a negative electrode facing the positive electrode, and a solid electrolyte layer between the positive electrode and the negative electrode.
  • the positive electrode has a positive electrode active material layer on a positive electrode current collector.
  • the negative electrode has a negative electrode active material layer on a negative electrode current collector. At least one of the negative electrode active material layer, the positive electrode active material layer, and the solid electrolyte layer is preferably formed of the solid electrolyte composition of the present invention.
  • the negative electrode active material layer and / or the positive electrode active material layer is more preferably formed of the solid electrolyte composition of the present invention
  • the positive electrode active material layer is more preferably formed of the solid electrolyte composition of the present invention.
  • the active material layer and / or the solid electrolyte layer formed of the solid electrolyte composition are preferably the same as those in the solid content of the solid electrolyte composition with respect to the component species to be contained and the content ratio thereof.
  • FIG. 1 is a cross-sectional view schematically showing an all solid state secondary battery (lithium ion secondary battery) according to a preferred embodiment of the present invention.
  • the all-solid-state secondary battery 10 of the present embodiment includes a negative electrode current collector 1, a negative electrode active material layer 2, a solid electrolyte layer 3, a positive electrode active material layer 4, and a positive electrode current collector 5 stacked in this order as viewed from the negative electrode side.
  • the adjacent layers are in direct contact with each other.
  • lithium ions (Li + ) accumulated in the negative electrode are returned to the positive electrode side, and electrons can be supplied to the working part 6.
  • a light bulb is adopted as a model for the operation site 6 and is lit by discharge.
  • any of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer is formed of the solid electrolyte composition of the present invention. That is, when the solid electrolyte layer 3 is formed of the solid electrolyte composition of the present invention, the solid electrolyte layer 3 includes an inorganic solid electrolyte and an anionic polymer.
  • the solid electrolyte layer usually does not contain a positive electrode active material and / or a negative electrode active material.
  • the solid electrolyte layer 3 it is considered that an anionic polymer chemically bonded to the inorganic solid electrolyte at the terminal exists between solid particles such as the inorganic solid electrolyte and the active material contained in the adjacent active material layer. . Therefore, the interfacial resistance between the solid particles is reduced and the binding property is increased.
  • the positive electrode active material layer 4 and / or the negative electrode active material layer 2 are formed of the solid electrolyte composition of the present invention, the positive electrode active material layer 4 and the negative electrode active material layer 2 are respectively a positive electrode active material or a negative electrode active material. And an inorganic solid electrolyte and an anionic polymer.
  • the active material layer contains an inorganic solid electrolyte
  • the ionic conductivity can be improved.
  • an anionic polymer chemically bonded to the inorganic solid electrolyte at the terminal exists between the solid particles. Therefore, the interfacial resistance between the solid particles is reduced and the binding property is increased.
  • the inorganic solid electrolyte and the anionic polymer contained in the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 may be the same or different from each other.
  • either or both of the positive electrode active material layer and the negative electrode active material layer may be simply referred to as an active material layer or an electrode active material layer.
  • One or both of the positive electrode active material and the negative electrode active material may be simply referred to as an active material or an electrode active material.
  • any one of the negative electrode active material layer, the positive electrode active material layer, and the solid electrolyte layer in the all-solid-state secondary battery includes the compound having the anion polymerizable functional group, solid particles such as an inorganic solid electrolyte, and the like. It is produced using a solid electrolyte composition containing For this reason, the binding property between solid particles can be improved, and as a result, good cycle characteristics in an all-solid secondary battery can also be realized. Although its action and mechanism are not clear but estimated, it can be considered as follows.
  • the all solid state secondary battery of the present invention exhibits high binding properties.
  • the contact between the solid particles is maintained by the covalent bond formed between the solid particle surface such as the inorganic solid electrolyte and the anionic polymer, and the interfacial resistance between the solid particles is reduced. The rise is considered to be suppressed.
  • the all-solid-state secondary battery of this invention shows the outstanding cycling characteristics. In particular, when active material particles that expand and contract due to charge and discharge are included, an increase in interfacial resistance between the solid particles is more effectively suppressed, and the all-solid-state secondary battery is considered to exhibit better cycle characteristics.
  • the thickness of the positive electrode active material layer 4, the solid electrolyte layer 3, and the negative electrode active material layer 2 is not particularly limited. Considering general battery dimensions, the thickness of each of the above layers is preferably 10 to 1,000 ⁇ m, more preferably 20 ⁇ m or more and less than 500 ⁇ m. In the all solid state secondary battery of the present invention, it is more preferable that the thickness of at least one of the positive electrode active material layer 4, the solid electrolyte layer 3 and the negative electrode active material layer 2 is 50 ⁇ m or more and less than 500 ⁇ m.
  • the positive electrode current collector 5 and the negative electrode current collector 1 are preferably electronic conductors. In the present invention, either or both of the positive electrode current collector and the negative electrode current collector may be simply referred to as a current collector.
  • Materials for forming the positive electrode current collector include aluminum, aluminum alloy, stainless steel, nickel and titanium, as well as the surface of aluminum or stainless steel treated with carbon, nickel, titanium or silver (formation of a thin film) Among them, aluminum and aluminum alloys are more preferable.
  • the material for forming the negative electrode current collector is treated with carbon, nickel, titanium or silver on the surface of aluminum, copper, copper alloy or stainless steel. What was made to do is preferable, and aluminum, copper, copper alloy, and stainless steel are more preferable.
  • the current collector is usually in the form of a film sheet, but a net, a punched one, a lath, a porous body, a foam, a fiber group molded body, or the like can also be used.
  • the thickness of the current collector is not particularly limited, but is preferably 1 to 500 ⁇ m.
  • the current collector surface is roughened by surface treatment.
  • a functional layer, a member, or the like is appropriately interposed or disposed between or outside each of the negative electrode current collector, the negative electrode active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector. May be.
  • Each layer may be composed of a single layer or a plurality of layers.
  • the basic structure of the all-solid-state secondary battery can be manufactured by arranging each of the above layers. Depending on the application, it may be used as an all-solid secondary battery as it is, but in order to form a dry battery, it is further enclosed in a suitable housing.
  • the housing may be metallic or made of resin (plastic). When using a metallic thing, the thing made from an aluminum alloy and stainless steel can be mentioned, for example.
  • the metallic housing is preferably divided into a positive-side housing and a negative-side housing, and electrically connected to the positive current collector and the negative current collector, respectively.
  • the casing on the positive electrode side and the casing on the negative electrode side are preferably joined and integrated through a gasket for preventing a short circuit.
  • a solid electrolyte-containing sheet containing an inorganic solid electrolyte and an anionic polymer by curing a coating film containing an inorganic solid electrolyte and a compound having an anion polymerizable functional group as the anionic polymerization proceeds Is formed.
  • an inorganic solid electrolyte acting as an anionic polymerization initiator is bonded to a polymer terminal.
  • the first aspect and the second aspect are preferably exemplified below.
  • 1st aspect The process (1 (alpha)) which apply
  • each said process is explained in full detail.
  • the anionic polymerization in the steps (1 ⁇ ) and (2 ⁇ ) proceeds slowly even at room temperature, but it is preferable to proceed by heating.
  • the coating film containing the inorganic solid electrolyte and the compound having an anion-polymerizable functional group becomes a gel, and is further cured as the anionic polymerization proceeds.
  • the curing means that the anionic polymerization is sufficiently progressed to be cured from a gel to a cured product.
  • the temperature is preferably 50 ° C. to 180 ° C., more preferably 80 ° C. to 150 ° C.
  • the heating time is preferably 5 minutes to 3 hours, more preferably 10 minutes to 1 hour.
  • the coating film and / or the sheet is dried simultaneously with the progress of the anionic polymerization, and a solid electrolyte-containing sheet from which the solvent component such as the dispersion medium is removed is obtained.
  • a step for removing a solvent component such as a dispersion medium is required separately.
  • the gap between the inorganic solid electrolyte particles formed in steps (2 ⁇ ) and (2 ⁇ ) is impregnated with a compound having an anion-polymerizable functional group, brought into contact, and then cured by the progress of anion polymerization. Is the method.
  • the inorganic solid electrolyte and the dispersion medium in the step (2 ⁇ ) can be preferably applied.
  • the slurrying conditions in the step (2 ⁇ ) the slurrying conditions described in the preparation of the solid electrolyte composition described above can be preferably applied.
  • the content of the inorganic solid electrolyte in the slurry is preferably 50 to 95% by mass, more preferably 5 to 90% by mass, and further preferably 60 to 90% by mass.
  • a component such as the above-mentioned active material, particle dispersant and binder (excluding a compound having an anion polymerizable functional group) is slurried in the presence of a dispersion medium. It is also preferable to make it.
  • the content of each component in the slurry the content in the above-mentioned solid electrolyte composition can be preferably applied.
  • the description of preparation of the said solid electrolytic composition is applicable about the process of slurry adjustment. That is, when the slurry obtained in the step (2 ⁇ ) contains a compound having an anionically polymerizable functional group, the step (2 ⁇ ) includes steps (a1) and (b1) in the preparation of the solid electrolytic composition. including.
  • the drying step can be appropriately adjusted depending on the dispersion medium and the like. For example, it is preferable to dry at 50 ° C. to 180 ° C. for 1 minute to 1 hour. Moreover, it is preferable to leave still and dry.
  • the thickness of the coating film formed in the step (2 ⁇ ) is not particularly limited, but is preferably adjusted to 20 ⁇ m to 500 ⁇ m in the step of impregnating the solution in the step (2 ⁇ ).
  • the solution of the compound having an anion polymerizable functional group in the step (2 ⁇ ) is a solution in which at least a compound having an anion polymerizable functional group is dissolved in a solvent.
  • the solvent is not particularly limited as long as it dissolves the compound having an anion polymerizable functional group, but the dispersion medium described in the above solid electrolyte composition can be preferably applied.
  • the concentration of the solution of the compound having an anion polymerizable functional group in the step (2 ⁇ ) is not limited as long as it can be impregnated in the gap between the inorganic solid electrolyte particles formed in the steps (2 ⁇ ) and (2 ⁇ ).
  • the mass is preferably from 10% by mass to 10% by mass.
  • a solid electrolyte-containing sheet that is a sheet having a base material and a solid electrolyte layer can be produced.
  • the method described in the production of the all-solid secondary battery can be used.
  • Manufacture of the all-solid-state secondary battery and the electrode sheet for all-solid-state secondary batteries can be performed by the manufacturing method of the said solid electrolyte containing sheet
  • the all-solid-state secondary battery can be produced by a conventional method except that the production method for the solid electrolyte-containing sheet is included.
  • the all-solid-state secondary battery and the all-solid-state secondary battery electrode sheet can be manufactured by forming each of the above layers using the solid electrolyte composition of the present invention.
  • any one of the positive electrode active material layer, the solid electrolyte layer, and the negative electrode active material layer may be produced by the above-described method for producing a solid electrolyte-containing sheet, and the other layers are solid electrolyte compositions that are not the present invention. And may be prepared by conventional methods. This will be described in detail below.
  • the all-solid-state secondary battery of the present invention includes (intervenes) a method in which the solid electrolyte composition of the present invention is applied onto a metal foil serving as a current collector and a coating film is formed (film formation).
  • a positive electrode active material layer is formed by applying a solid electrolyte composition containing a positive electrode active material as a positive electrode material (positive electrode layer composition) on a metal foil that is a positive electrode current collector.
  • a positive electrode sheet for a secondary battery is prepared.
  • a solid electrolyte composition for forming a solid electrolyte layer is applied on the positive electrode active material layer to form a solid electrolyte layer.
  • a solid electrolyte composition containing a negative electrode active material is applied as a negative electrode material (negative electrode layer composition) on the solid electrolyte layer to form a negative electrode active material layer.
  • An all-solid secondary battery having a structure in which a solid electrolyte layer is sandwiched between a positive electrode active material layer and a negative electrode active material layer is obtained by stacking a negative electrode current collector (metal foil) on the negative electrode active material layer. Can do. If necessary, this can be enclosed in a housing to obtain a desired all-solid secondary battery.
  • each layer is reversed, and a negative electrode active material layer, a solid electrolyte layer, and a positive electrode active material layer are formed on the negative electrode current collector, and the positive electrode current collector is stacked to manufacture an all-solid secondary battery.
  • Another method includes the following method. That is, a positive electrode sheet for an all-solid secondary battery is produced as described above. Further, a negative electrode active material layer is formed by applying a solid electrolyte composition containing a negative electrode active material as a negative electrode material (a composition for a negative electrode layer) on a metal foil that is a negative electrode current collector. A negative electrode sheet for a secondary battery is prepared. Next, a solid electrolyte layer is formed on one of the active material layers of these sheets as described above. Furthermore, the other of the positive electrode sheet for an all solid secondary battery and the negative electrode sheet for an all solid secondary battery is laminated on the solid electrolyte layer so that the solid electrolyte layer and the active material layer are in contact with each other.
  • Another method includes the following method. That is, as described above, a positive electrode sheet for an all-solid secondary battery and a negative electrode sheet for an all-solid secondary battery are produced. Separately from this, a solid electrolyte composition is applied on a substrate to produce a solid electrolyte sheet for an all-solid secondary battery comprising a solid electrolyte layer. Furthermore, it laminates
  • An all-solid-state secondary battery can also be manufactured by a combination of the above forming methods. For example, as described above, a positive electrode sheet for an all-solid secondary battery, a negative electrode sheet for an all-solid secondary battery, and a solid electrolyte sheet for an all-solid secondary battery are produced. Subsequently, after laminating the solid electrolyte layer peeled off from the base material on the negative electrode sheet for an all solid secondary battery, an all solid secondary battery can be manufactured by pasting the positive electrode sheet for the all solid secondary battery. it can. In this method, the solid electrolyte layer can be laminated on the positive electrode sheet for an all-solid secondary battery, and bonded to the negative electrode sheet for an all-solid secondary battery.
  • the method for applying the solid electrolyte composition is not particularly limited, and can be appropriately selected. Examples thereof include coating (preferably wet coating), spray coating, spin coating coating, dip coating, slit coating, stripe coating, and bar coating coating. At this time, the solid electrolyte composition may be dried after being applied, or may be dried after being applied in multiple layers.
  • the drying temperature is not particularly limited.
  • the lower limit is preferably 30 ° C or higher, more preferably 60 ° C or higher, and still more preferably 80 ° C or higher.
  • the upper limit is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 200 ° C. or lower.
  • a dispersion medium By heating in such a temperature range, a dispersion medium can be removed and it can be set as a solid state. Moreover, it is preferable because the temperature is not excessively raised and each member of the all-solid-state secondary battery is not damaged. Thereby, in the all-solid-state secondary battery, excellent overall performance can be exhibited and good binding properties can be obtained.
  • each layer or all-solid secondary battery After applying the solid electrolyte composition or after producing the all-solid-state secondary battery. Moreover, it is also preferable to pressurize in the state which laminated
  • An example of the pressurizing method is a hydraulic cylinder press.
  • the applied pressure is not particularly limited and is generally preferably in the range of 50 to 1500 MPa. Moreover, you may heat the apply
  • the heating temperature is not particularly limited, and is generally in the range of 30 to 300 ° C. It is also possible to press at a temperature higher than the glass transition temperature of the inorganic solid electrolyte.
  • the pressurization may be performed in a state where the coating solvent or the dispersion medium is previously dried, or may be performed in a state where the solvent or the dispersion medium remains.
  • each composition may be apply
  • the atmosphere during pressurization is not particularly limited, and may be any of the following: air, dry air (dew point -20 ° C. or lower), and inert gas (for example, argon gas, helium gas, nitrogen gas).
  • the pressing time may be a high pressure in a short time (for example, within several hours), or a medium pressure may be applied for a long time (1 day or more).
  • a restraining tool screw tightening pressure or the like
  • the pressing pressure may be uniform or different with respect to the pressed part such as the sheet surface.
  • the pressing pressure can be changed according to the area and film thickness of the pressed part. Also, the same part can be changed stepwise with different pressures.
  • the press surface may be smooth or roughened.
  • the all solid state secondary battery manufactured as described above is preferably initialized after manufacture or before use.
  • the initialization is not particularly limited, and can be performed, for example, by performing initial charging / discharging in a state where the press pressure is increased, and then releasing the pressure until the general use pressure of the all-solid secondary battery is reached.
  • the all solid state secondary battery of the present invention can be applied to various uses. Although there is no particular limitation on the application mode, for example, when installed in an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile fax machine, a mobile phone Copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, mini-disc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio and backup power source.
  • Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, and medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military uses or space use. Moreover, it can also combine with a solar cell.
  • An all-solid secondary battery refers to a secondary battery in which the positive electrode, the negative electrode, and the electrolyte are all solid. In other words, it is distinguished from an electrolyte type secondary battery using a carbonate-based solvent as an electrolyte.
  • this invention presupposes an inorganic all-solid-state secondary battery.
  • the all-solid-state secondary battery includes an organic (polymer) all-solid-state secondary battery using a polymer compound such as polyethylene oxide as an electrolyte, and an inorganic all-solid-state using the above-described Li—PS glass, LLT, LLZ, etc. It is divided into secondary batteries.
  • the inorganic solid electrolyte is distinguished from the above-described electrolyte (polymer electrolyte) using a polymer compound such as polyethylene oxide as an ion conductive medium, and the inorganic compound serves as an ion conductive medium. Specific examples include the above-described Li—PS glass, LLT, and LLZ.
  • the inorganic solid electrolyte itself does not release cations (Li ions) but exhibits an ion transport function.
  • a material that is added to the electrolytic solution or the solid electrolyte layer and serves as a source of ions that release cations is sometimes called an electrolyte, but it is distinguished from the electrolyte as the ion transport material.
  • electrolyte salt or “supporting electrolyte”.
  • the electrolyte salt include LiTFSI (lithium bistrifluoromethanesulfonylimide).
  • composition means a mixture in which two or more components are uniformly mixed. However, as long as the uniformity is substantially maintained, aggregation or uneven distribution may partially occur within a range in which a desired effect is achieved.
  • a solid electrolyte composition when it is referred to as a solid electrolyte composition, it basically refers to a composition (typically a paste) that is a material for forming a solid electrolyte layer or the like, and an electrolyte layer or the like formed by curing the composition. Shall not be included in this.
  • Example 1 ⁇ Preparation example of solid electrolyte composition>
  • Into a 45 mL zirconia container manufactured by Fritsch, 180 pieces of zirconia beads having a diameter of 5 mm are charged, 9.0 g of an inorganic solid electrolyte and 18 g of a dispersion medium are added, and then the container is set on a planetary ball mill P-7 manufactured by Fritsch. And mixing at a rotation speed of 300 rpm for 2 hours. To this, 0.36 g of an additive was added, and further mixing was continued at 150 rpm for 5 minutes to prepare solid electrolyte compositions S-1 to S-10, T-1 and T-2.
  • solid electrolyte composition T-2 was charged with 0.036 g (not shown in the table) of perhexyl D (thermal radical polymerization initiator, manufactured by NOF Corporation) at the same timing as the charging of the active material. And mixed to prepare a solid electrolyte composition.
  • Table 1 shows the components and blending mass ratios of each solid electrolyte composition.
  • LLT Li 0.5 La 0.5 TiO 3 (manufactured by Toshima Seisakusho)
  • LPS Li—PS system glass LLZ synthesized above: Li 7 La 3 Zr 2 O 12
  • LCO LiCoO 2 (lithium cobaltate)
  • NCA LiNi 0.85 Co 0.10 Al 0.05 O 2 (nickel cobalt lithium aluminum oxide)
  • B-1 Ethyl 2-cyanoacrylate
  • B-2 Butyl 2-trifluoromethyl acrylate
  • B-3 Diethyl 2-methylenemalonate
  • B-4 Bis (2-trifluoromethylacrylic acid) -1,4 -Butanediyl
  • E-1 acrylic acid
  • Binding Test A 180 ° peel strength test (JIS Z0237-2009) was performed on the obtained solid electrolyte-containing sheet.
  • An adhesive tape (width 24 mm, length 300 mm) (trade name: Cellotape (registered trademark) CT-24, manufactured by Nichiban Co., Ltd.) was attached to the surface of the solid electrolyte-containing sheet on which the solid electrolyte composition was cured.
  • the present invention containing an inorganic solid electrolyte and a specific anionic polymer produced using the solid electrolyte composition of the present invention containing an inorganic solid electrolyte and a compound having an anion polymerizable functional group.
  • the solid electrolyte containing sheet had high adhesion and excellent binding properties.
  • seat excellent in binding property was able to be produced with the manufacturing method of the solid electrolyte containing sheet
  • c11 is a sheet prepared in advance using a comparative solid electrolyte composition T-1 containing a cyano group-containing polymer, which is a polymer, and does not contain a specific anionic polymer.
  • This solid electrolyte-containing sheet No. c11 had low adhesion and insufficient binding properties. This is probably because the dispersibility of the cyano group-containing polymer is low, and no chemical bond is formed between the inorganic solid electrolyte and the polymer.
  • the solid electrolyte-containing sheet No. c12 is a sheet produced using the comparative solid electrolyte composition T-2 containing a radical polymerizable monomer, and does not contain a specific anionic polymer. This solid electrolyte-containing sheet No.
  • c12 had low adhesive force and its binding property was not sufficient. This is probably because no chemical bond is formed between the inorganic solid electrolyte and the radical polymer. Moreover, the solid electrolyte containing sheet No. produced without using the manufacturing method of the solid electrolyte containing sheet of this invention. c11 and c12 were inferior in binding property.
  • Each all-solid secondary battery after initialization was charged at a current density of 0.2 mA / cm 2 until the battery voltage reached 4.2 V, then the battery voltage at a current density of 0.2 mA / cm 2 2.5V Discharged until reached. This charging / discharging was made into 1 cycle, and charging / discharging was repeated. In this charge / discharge cycle, the number of cycles when the discharge capacity reached less than 80 when the discharge capacity in the first cycle after initialization was set to 100 was evaluated according to the following criteria. In addition, evaluation "C" or more is a pass level of this test.
  • a positive electrode layer not containing a specific anionic polymer was formed using a comparative solid electrolyte composition T-1 containing a cyano group-containing polymer which is a polymer in advance.
  • This all-solid-state secondary battery No. c21 did not have sufficient cycle characteristics. This is probably because the dispersibility of the cyano group-containing polymer is low, and no chemical bond is formed between the inorganic solid electrolyte and the polymer. All solid state secondary battery No. for comparison.
  • a positive electrode layer not containing a specific anion polymer was formed using a comparative solid electrolyte composition T-2 containing a radical polymerizable monomer. This all-solid-state secondary battery No.
  • c22 did not have sufficient cycle characteristics. This is probably because no chemical bond is formed between the inorganic solid electrolyte and the radical polymer. Moreover, the all-solid-state secondary battery No. 1 for comparison produced without going through the method for producing the solid electrolyte-containing sheet of the present invention was used. c21 and c22 did not have sufficient cycle characteristics.

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Abstract

La présente invention concerne une composition d'électrolyte solide qui contient un électrolyte solide inorganique ayant une conductivité d'ions d'un métal du groupe 1 ou du groupe 2 de la table périodique et un composé ayant un groupe fonctionnel polymérisable par voie anionique ; une feuille contenant un électrolyte solide qui comprend un électrolyte solide inorganique ayant une conductivité d'ions d'un métal du groupe 1 ou du groupe 2 de la table périodique et un polymère anionique spécifique qui est lié à l'électrolyte solide inorganique ; une batterie rechargeable entièrement solide ; un procédé de production d'une composition d'électrolyte solide ; un procédé de production d'une feuille contenant un électrolyte solide ; et un procédé de fabrication d'une batterie rechargeable entièrement solide.
PCT/JP2017/008845 2016-03-08 2017-03-06 Composition d'électrolyte solide, feuille contenant un électrolyte solide, batterie rechargeable entièrement solide, procédé de production de composition d'électrolyte solide, procédé de production de feuille contenant un électrolyte solide, et procédé de fabrication de batterie rechargeable entièrement solide WO2017154851A1 (fr)

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CN201780015831.8A CN108780918B (zh) 2016-03-08 2017-03-06 固体电解质组合物、含有固体电解质的片材、全固态二次电池以及这些的制造方法
US16/123,023 US10833351B2 (en) 2016-03-08 2018-09-06 Solid electrolyte composition, solid electrolyte-containing sheet, all-solid state secondary battery, and methods for manufacturing solid electrolyte composition, solid electrolyte-containing sheet, all-solid state secondary battery

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US11522216B2 (en) 2018-01-05 2022-12-06 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery
JP2019125468A (ja) * 2018-01-16 2019-07-25 トヨタ自動車株式会社 リチウム電池用負極スラリー
WO2020022195A1 (fr) * 2018-07-27 2020-01-30 富士フイルム株式会社 Composition d'électrolyte solide, feuille contenant un électrolyte solide, batterie rechargeable tout solide, et procédés de production de feuille contenant un électrolyte solide et de batterie rechargeable tout solide
CN112292779A (zh) * 2018-07-27 2021-01-29 富士胶片株式会社 固体电解质组合物、含固体电解质的片材及全固态二次电池、以及后两者的制造方法
JPWO2020022195A1 (ja) * 2018-07-27 2021-04-08 富士フイルム株式会社 固体電解質組成物、固体電解質含有シート、及び全固体二次電池、並びに固体電解質含有シート及び全固体二次電池の製造方法
JP2020021655A (ja) * 2018-08-01 2020-02-06 株式会社日本触媒 電解液、アルカリ金属イオン二次電池、及び電解液用添加剤
JP7251934B2 (ja) 2018-08-01 2023-04-04 株式会社日本触媒 電解液、アルカリ金属イオン二次電池、及び電解液用添加剤

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JPWO2017154851A1 (ja) 2019-01-17
US20190006700A1 (en) 2019-01-03

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